Facile Synthesis of 1,4-Diketones via Palladium Complex Catalyzed Isomerization of Alkynediols

Article abstract of DOI:10.1021/jo00020a015

Alkynediols isomerized under the catalysis of Pd(dba)3*CHCl3 + 2n-Bu3P in acetonitrile at 80 deg C to give 1,4-diketones in high yields.This experimentally simple and economically synthetic method is illustrated with examples including substituents such as alkyl, alkenyl, and aryl groups.The order of reactivity of the substituents in this reaction is aryl >/= alkenyl > alkyl.Alkenyl-substituted alkynediols chemoselectively isomerized to the corresponding α,β-unsaturated 1,4-diketones.The usefulness of this novel method is examplified by the synthesis of dihydrojasmone.